EP0563704A1 - Film polymérique détachable - Google Patents

Film polymérique détachable Download PDF

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Publication number
EP0563704A1
EP0563704A1 EP19930104542 EP93104542A EP0563704A1 EP 0563704 A1 EP0563704 A1 EP 0563704A1 EP 19930104542 EP19930104542 EP 19930104542 EP 93104542 A EP93104542 A EP 93104542A EP 0563704 A1 EP0563704 A1 EP 0563704A1
Authority
EP
European Patent Office
Prior art keywords
segments
layer
reactive
film
release
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19930104542
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German (de)
English (en)
Other versions
EP0563704B1 (fr
Inventor
Richard Paul Pankratz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
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Publication of EP0563704A1 publication Critical patent/EP0563704A1/fr
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Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
    • C09J2400/226—Presence of unspecified polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2839—Web or sheet containing structurally defined element or component and having an adhesive outermost layer with release or antistick coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31562—Next to polyamide [nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31721—Of polyimide

Definitions

  • This invention relates to a polymeric film with release properties and to a method for the production thereof. More particularly, it relates to a polymeric film substrate with a silicone release layer, in which the adhesion of the silicone release layer to the substrate is improved.
  • release films have been used in a wide variety of applications.
  • release films are used as protective coversheets for photosensitive materials, as release layers for pressure sensitive adhesives, as temporary supports for decorative decals and stickers, etc.
  • release films comprise a polymeric film substrate coated with a silicone release layer.
  • the silicone release layer is generally a coating of a cured, i.e., crosslinked, polysiloxane resin. While such coatings exhibit good release properties, the anchorage of the silicone resin to the polymeric film substrate has been found to be unsatisfactory. In extreme cases, where the silicone composition is cured under conditions of high humidity, the resultant layer is readily removed when rubbed with one's fingers.
  • the adhesion of the silicone resin to the film substrate is often improved by applying a surface treatment to the substrate prior to coating the silicone resin.
  • Surface treatments which have been used include treatment with a flame or a corona discharge.
  • some of the silicone transfers to the backside of the film.
  • a release film comprising a self-supporting, polymeric film substrate having on at least one surface thereof, a polymeric abherent layer wherein the abherent layer comprises a polyurethane resin which is the reaction product of (i) an organic polyisocyanate, (ii) an isocyanate reactive polydialkylsiloxane, and (iii) a polymeric polyol.
  • the abherent layer adheres firmly to the film substrate but provides release from an opposing surface.
  • the present invention provides a release film comprising in order:
  • a release film comprising in order (a) a polymeric film substrate (b) a primer layer containing a polymer having reactive segments and polysiloxane segments and (c) a silicone release layer. Adhesion is improved between all three layers, i.e., adhesion is improved between the film substrate and the primer layer and between the primer layer and the overlying silcone release layer.
  • a polymeric film substrate is first coated with a primer layer, which is then overcoated with a silicone release layer.
  • the primer layer contains a polymer which has both reactive segments and polysiloxane segments.
  • the primer layer contains a crosslinking agent which reacts with the polymer in a subsequent hardening or curing step.
  • silicone release layer it is meant a layer of an organopolysiloxane, including any of those organopolysiloxane compounds which are known to have low surface energy and low adhesive properties.
  • the substrate is a dimensionally stable, self-supporting polymeric film which remains stable throughout the processing conditions.
  • self-supporting refers to a film that does not have to be supported by a web or other carrier.
  • suitable films include cellulosic films and thermoplastic materials such as polyolefins, polyamides, polyimides and polyesters. Linear polyesters are preferred, particularly polyethylene terephthalate (PET).
  • polyester films can also serve as the substrate, including, for example, ethylene glycol polyesters of isophthalic acid, of naphthalenic acid, or of mixtures of terephthalic and naphthalenic and/or isophthalic acids; or polyesters of other glycols, especially of butanediol, 1,4-cyclohexane dimethanol, or mixtures of ethylene glycol with butanediol.
  • film encompasses films, sheets tapes, disks and similar commercial articles.
  • the thickness of the film substrate will depend on the intended use of the final release film. Typically, the final release film has a thickness in the range of about 0.25 to about 15 mils (6 to 375 micrometers).
  • the film substrate can be treated to improve its adhesive properties.
  • Typical adhesion-promoting treatments include flame treatments and corona discharge treatments.
  • the polymeric film substrate is coated with a composition which comprises an organic polymer having reactive segments and polysiloxane segments.
  • the polymer having reactive segments and polysiloxane segments is generally a block copolymer.
  • the reactive and/or polysiloxane segments can be present in the polymer backbone or in the form of pendant groups.
  • the reactive segment contains groups capable of reacting with the crosslinking agent and provides much of the adhesive function for the primer layer. Examples of suitable reactive functional groups include, but are not limited to, carboxyl, hydroxyl, amine, amide, or oxirane groups.
  • polymers which can be used as the reactive segment include polycarbonates; polymers and copolymers of unsaturated acids and anhydrides, such as acrylic acid, methacrylic acid, maleic anhydride and highly carboxylated polyolefins; polyvinyl alcohol and partially hydrolyzed polyvinyl acetate; hydroxy or amino substituted polyacrylates and polymethacrylates; polyacrylamide; and epoxy polymers.
  • the reactive segment can also be incorporated as a polymeric side chain on, for example, a polyolefin or vinyl polymer.
  • the reactive groups generally comprise about 0.01 to 5.0% by weight, based on the total weight of the reactive segment, although higher levels can be used.
  • the polysiloxane segment can be a part of the polymer backbone or a polymeric side chain.
  • the polysiloxane is preferably a polydialkylsiloxane in which the alkyl group has from 1 to 6 carbon atoms. Particularly preferred is polydimethylsiloxane.
  • the organic polymer and the different segments are prepared by polymerization techniques which are well known in the art.
  • the polysiloxane segment generally comprises from about 10 to 90% by weight of the polymer, preferably 30 to 70%, by weight.
  • a particularly preferred polymer is the reaction product of a polycarbonate polyol, an organic polyisocyanate, and an isocyanate-reactive polydialkylsiloxane.
  • the primer layer is a thermally hardened layer which is the reaction product of (i) an organic polymer having reactive segments and polysiloxane segments, (ii) a crosslinking agent and (iii) a catalyst.
  • the crosslinking agent is a polyfunctional compound which will react with the reactive segments of the organic polymer in a hardening or curing step.
  • suitable crosslinking agents include melamine-formaldehyde, urea-formaldehyde, benzoguanamine-formaldehyde, glycoluril-formaldehyde, epoxy and aziridine resins.
  • a preferred crosslinking agent is melamine-formaldehyde resin. The resin is used in an amount of about 1-25% by weight, based on the weight of the organic polymer.
  • the catalyst functions to accelerate the crosslinking reaction.
  • Preferred catalysts for crosslinking most formaldehyde based resins include ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium thiocyanate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, para-toluene sulfonic acid, sulfuric acid, maleic acid stabilized by reaction with a base, ammonium para-toluene sulfonate and morpholinium para-toluene sulfonate.
  • the catalyst is generally present in an amount of about 1-20% by weight based on the weight of the crosslinking agent.
  • the primer layer composition can also contain other additives as long as they do not interfere with the adhesive properties of the coating.
  • additives which may be present include wetting agents, rheology control agents, solubility aids, surfactants, and the like.
  • the primer composition include a surfactant, e.g., sodium lauryl sulfate, sodium salt of dioctyl sulfosuccinate, nonylphenol polyethylene glycol ethers and ammonium lauryl ether sulfates.
  • the primer layer composition can be applied from a solvent or aqueous carrier. It is preferred that the primer be applied as an aqueous emulsion to the polymeric film substrate.
  • the emulsion is prepared using standard techniques which are well known.
  • the primer layer composition can be applied to the substrate during or after film manufacture.
  • the primer can be coated onto the film substrate in the form of a solution, dispersion or emulsion, using any conventional coating process.
  • the primer is in the form of an aqueous emulsion, and is coated onto an unstretched or uniaxially or biaxially stretched polyester film, especially PET. This can be accomplished, for example, by passing the polyester film through a bath of the primer emulsion, i.e., coating the primer layer on both sides of the polymeric film substrate, or by applying the emulsion to one side only with a roller or a brush.
  • the coated material is then dried, and the coated film is stretched, if desired, and heated to a sufficient temperature to promote crosslinking of the organic polymer with the crosslinking agent. Typically, a temperature of from about 150 to 250°C is used for curing. If the coating is applied to an unstretched film, or unidirectionally stretched film, the film can be stretched following the coating step without loss of the mechanical integrity of the coating and then heated to a sufficient temperature to promote crosslinking.
  • the thickness of the primer layer, after drying and stretching should be about 0.01 to 1.0 micrometers, preferably 0.03 to 0.06 micrometers. The usual amount of coating material is about 0.03 to 0.06 g/m2 of film surface.
  • the primer layer can be applied to both sides of the polymeric film substrate. If the primer layer is only coated on one side of the polymeric film substrate, the side opposite the primer may be (a) untreated, (b) treated to improve adhesive properties inluding flame treatment or corona discharge, or (c) coated with a functional layer as is known in the art to provide specific end use requirements including heat seal or adhesive properties.
  • An advantage of the present invention is that the choice of silicone release material is not limited by the adhesive properties of the film substrate. Accordingly, any of the different types of commercial silicone compositions can be used, with good adhesion to the primer-coated substrate.
  • the silicone release material can be 100% solid, or solvent or aqueous based.
  • the material can be cured thermally, or by exposure to electron beam or ultraviolet radiation.
  • Reactions to produce the silicone release layer include, but are not limited to: (1) addition reactions between polysiloxanes with pendant vinyl groups and polysiloxanes containing silicon hydrides catalyzed by metals such at Pt or Rh compounds; (2) condensation reactions between silanol-containing polysiloxanes and hydrogen polysiloxanes catalyzed by tin compounds; (3) polysiloxanes with pendant unsaturated groups, such as acrylate or methacrylates, cured through addition reactions initiated by EB, UV, or thermal mechanisms; and (4) polysiloxanes with pendant epoxy groups, such as glycidylmethacrylate, cured through addition reactions where the acid catalyst is generated via UV decomposition of an acid precursor.
  • Suitable silicone materials are commercially available from a number of different suppliers.
  • the silicone release material can be coated onto the primer-coated film substrate in the form of a solution, dispersion or emulsion, using any conventional coating process. After coating, the compositions can be dried and cured by passing through tunnel ovens heated to about 60-210°C for times varying from 2 to 30 seconds.
  • the amount of silicone release material coated depends on the proportion of silicone resin in the coating composition and on the specific release properties desired in the final release film. In general, a dry coating weight of from 0.05 to 10 mg/cm2 is acceptable.
  • Example 1 The following procedure was followed for Example 1 and Comparative Examples 1-3:
  • a cast polyethylene terephthalate film was stretched in the machine direction and corona treated.
  • An aqueous emulsion of a primer coating was then applied to the film by roller coating.
  • the coating was dried at 70°C for 4 seconds, and the coated film was further stretched in the transverse direction.
  • the film was subsequently heated at 200°C for 2 seconds to heat set the polyester and to cure the primer composition.
  • the final coating thickness of the primer layer was .035 micrometers; and the final thickness of the film was 1 mil (25 micrometers).
  • a standard silicone release layer was then applied to the dried primer-coated polyester film substrate.
  • the silicone release layer was cured according to conventional methods.
  • the adhesion of the silicone release layer to the primer-coated polyester film substrate was determined by rubbing one's fingers across the surface of the release layer while applying moderate pressure. Adhesion was considered to be “good” if the layer was not removed by the rubbing. Adhesion was considered to be “poor” if any of the silicone release layer was removed.
  • a primer coating containing a polycarbonate-polysiloxane-polyurethane polymer, which is carboxy-functional, and a crosslinker was prepared by placing the components listed below in a 5 gal. vessel and mixing with a rod until a homogeneous mixture was obtained.
  • the polymer used was Permuthane® UE-41222, supplied by Permuthane Coatings (Peabody, MA), as a 30% solids emulsion in water.
  • the primer coating had the following composition: Component Amount (g) Polymer 2826 Crosslinker solution (below) 225 Water to 11.3 kg
  • crosslinker solution was prepared from the components listed below.
  • Component Amount (g) Crosslinker 235.5 Surfactant I 342.5 Surfactant II 62.8 Ammonium hydroxide 130 Isopropanol 942 Ammonium sulfate 35.3 Water to 2500 g
  • the primer coating was applied to the corona treated polyester substrates and then dried. Samples of the primer-coated polyester substrate were subsequently overcoated with the following silicone release layers: (A) a solvent based silicone release composition with a Pt catalyst which was heat cured; (B) a low release commercial silicone release layer which was heat cured; (C) a high release commercial silicone release layer which was heat cured; and (D) a high release, high MW commercial silicone release layer which was heat cured.
  • a primer coating was prepared using a polymer which did not contain polysiloxane segments.
  • the polymer used was a copolymer of styrene, butyl acrylate, methyl methacrylate and methacrylic acid which was supplied as a 41.5% solids aqueous emulsion (Rhoplex® WL-81 from Rohm and Haas, Philadelphia, PA).
  • the primer coating had the following composition: Component Amount (g) Polymer 2043 Crosslinker Solution 225 Water to 11.3 kg
  • the crosslinker solution was the same as that described in Example 1.
  • the primer coating was applied to a corona treated polyester substrate and then dried. Samples of the primer-coated polyester substrate were subsequently coated with the same silicone release layers described in Example 1. The adhesion of the silicone release layer to the primer-coated polyester substrate was determined and the results are provided in Table 1 below.
  • a primer coating was prepared using a polymer which did not contain polysiloxane segments.
  • the polymer used was a copolymer of ethylene glycol, isophthalic acid and the sodium salt of 5-sulfoisophthalic acid which was supplied as a 28% solids aqueous solution (AQ 55D from Tennessee Eastman, Kingsport, TN).
  • the primer coating had the following composition: Component Amount (g) Polymer 3027 Crosslinker Solution 225 Water to 11.3 kg
  • the crosslinker solution was the same as that described in Example 1.
  • the primer coating was applied to the corona treated polyester substrates and then dried. Samples of the primer-coated polyester substrate were subsequently coated with the same silicone release layers described in Example 1. The adhesion of the silicone release layer to the primer-coated polyester substrate was determined and the results are provided in Table 1 below.
  • a primer coating was prepared using a polymer which did not contain polysiloxane segments.
  • the polymer used was a copolymer of methyl methacrylate, ethyl acrylate and methacrylamide supplied as a 46% solids aqueous emulsion.
  • the emulsion contained, on a solids basis, about 25% melamine formaldehyde resin on acrylic resin (Rhoplex® AC201 from Rohm and Haas, Philadelphia, PA).
  • the primer coating had the following composition: Component Amount (g) Polymer 2451 Dimethylamino ethanol 22.5 Water to 11.3 kg
  • the adhesion of the silicone release layer was good for each type of silicone resin used in the polymeric release films of Example 1.
  • the films of Comparative Examples 1-3 and the uncoated polyethylene terephthalate exhibited poor adhesion.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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EP19930104542 1992-03-31 1993-03-19 Film polymérique détachable Expired - Lifetime EP0563704B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US860838 1992-03-31
US07/860,838 US5415935A (en) 1992-03-31 1992-03-31 Polymeric release film

Publications (2)

Publication Number Publication Date
EP0563704A1 true EP0563704A1 (fr) 1993-10-06
EP0563704B1 EP0563704B1 (fr) 1996-10-02

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US (1) US5415935A (fr)
EP (1) EP0563704B1 (fr)
JP (1) JP2512858B2 (fr)
KR (1) KR930019401A (fr)
CA (1) CA2091083A1 (fr)
DE (1) DE69305101T2 (fr)

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EP0776928A1 (fr) * 1995-11-21 1997-06-04 Imperial Chemical Industries Plc Film polymère
US5910370A (en) * 1995-11-21 1999-06-08 Ici Americas Inc Polymeric film
WO2000027900A1 (fr) * 1998-11-11 2000-05-18 Minnesota Mining And Manufacturing Company Feuille multicouche revetue d'une couche protectrice de polyurethane
WO2004071765A2 (fr) * 2003-02-12 2004-08-26 General Electric Company Compositions de liberation pour le papier adherant mieux au papier et aux films polymeres
US7479522B2 (en) 2005-11-09 2009-01-20 Momentive Performance Materials Inc. Silicone elastomer composition
WO2009147283A1 (fr) * 2008-06-03 2009-12-10 Upm-Kymmene Corporation Composition de revêtement de démoulage, matériau de base et procédé de fabrication d'un matériau de base, et agent de traitement de surface pour matériau de base et utilisation d'un agent de traitement de surface
US7767754B2 (en) 2005-11-08 2010-08-03 Momentive Performance Materials Inc. Silicone composition and process of making same
WO2010116045A1 (fr) * 2009-04-09 2010-10-14 Upm-Kymmene Corporation Procédé de traitement d'une surface d'un substrat
CN103254751A (zh) * 2011-07-12 2013-08-21 苏州斯迪克新材料科技股份有限公司 胶带用雾面离型膜的制作工艺
CN106221595A (zh) * 2016-07-21 2016-12-14 苏州泰仑电子材料有限公司 超轻离型力的离型膜及其制备方法

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US5932352A (en) * 1995-11-21 1999-08-03 Higgins; David Edward Release film
JP3005620B2 (ja) * 1996-03-28 2000-01-31 レフライト株式会社 インキ汚れ防止シート
US5910535A (en) * 1996-05-03 1999-06-08 Decora, Incorporated Water based coating composition having sacrificial layer for stain removal
JPH1180678A (ja) * 1997-09-16 1999-03-26 Lintec Corp 付着シート
KR100558567B1 (ko) * 1998-01-08 2006-06-21 도레이새한 주식회사 이축연신 폴리에스테르 필름의 제조방법
AU6416399A (en) 1998-10-01 2000-04-17 Airtech International, Inc. Method of molding or curing a resin material at high temperatures using a multilayer release film
US6990904B2 (en) * 2000-10-31 2006-01-31 International Imaging Materials, Inc Thermal transfer assembly for ceramic imaging
US6811863B2 (en) 2001-07-20 2004-11-02 Brite Ideas, Inc. Anti-marking coverings for printing presses
JP2005231355A (ja) * 2004-01-23 2005-09-02 Shin Etsu Chem Co Ltd 剥離フィルム
KR100965378B1 (ko) * 2005-12-07 2010-06-22 도레이첨단소재 주식회사 박리력을 조절할 수 있는 실리콘 이형 조성물 및 이를 코팅한 실리콘 이형필름
JP2009012317A (ja) * 2007-07-05 2009-01-22 Shin Etsu Chem Co Ltd 剥離フィルムおよびその製造方法
DE102008036518A1 (de) * 2008-08-06 2010-02-11 Tesa Se Verwendung eines Organopolysiloxan/Polyharnstoff-Blockcopolymers als Beschichtung auf Kunststoff-Oberflächen
WO2011043386A1 (fr) * 2009-10-06 2011-04-14 ソニーケミカル＆インフォメーションデバイス株式会社 Composition d'agent antiadhésif, film antiadhésif et film adhésif obtenus à l'aide de celle-ci
DE102010049022A1 (de) * 2010-10-21 2012-04-26 Kendrion Binder Magnete Gmbh Hochdruckregelventil
WO2015137933A1 (fr) 2014-03-12 2015-09-17 Bemis Company, Inc. Film d'emballage pourvu d'un revêtement empêchant l'adhérence du produit
US10611123B2 (en) 2015-02-20 2020-04-07 3M Innovative Properties Company Silicone carbonate polymers as release layers for pressure sensitive adhesive containing articles
ITMI20150550A1 (it) * 2015-04-16 2016-10-16 Siliconature S P A Procedimento per la siliconatura di pellicole di polietilene tereftalato (pet).
JP6745153B2 (ja) * 2016-07-11 2020-08-26 信越ポリマー株式会社 導電性離型層形成用塗料及びその製造方法、並びに導電性離型フィルム及びその製造方法
JP6493628B2 (ja) * 2017-03-24 2019-04-03 住友ベークライト株式会社 モールド成形用離型フィルム及びモールド成形方法
US20220145141A1 (en) * 2019-03-29 2022-05-12 3M Innovative Properties Company Article

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EP0325210A2 (fr) * 1988-01-18 1989-07-26 Nitto Denko Corporation Agent de démoulage et composite ayant une couche d'agent de démoulage vulcanisé
EP0382094A2 (fr) * 1989-02-01 1990-08-16 Kanegafuchi Chemical Industry Co., Ltd. Méthode d'adhésion
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EP0776928A1 (fr) * 1995-11-21 1997-06-04 Imperial Chemical Industries Plc Film polymère
US5910370A (en) * 1995-11-21 1999-06-08 Ici Americas Inc Polymeric film
US6383644B2 (en) 1998-11-11 2002-05-07 3M Innovative Properties Company Multi-layer sheet comprising a protective polyurethane layer
EP1004608A1 (fr) * 1998-11-11 2000-05-31 Minnesota Mining And Manufacturing Company Feuille multi-couches comprenant une couche protectrice de polyuréthane
WO2000027900A1 (fr) * 1998-11-11 2000-05-18 Minnesota Mining And Manufacturing Company Feuille multicouche revetue d'une couche protectrice de polyurethane
US8343632B2 (en) 2003-02-12 2013-01-01 Momentive Performance Materials Inc. Paper release compositions having improved adhesion to paper and polymeric films
WO2004071765A2 (fr) * 2003-02-12 2004-08-26 General Electric Company Compositions de liberation pour le papier adherant mieux au papier et aux films polymeres
WO2004071765A3 (fr) * 2003-02-12 2004-10-28 Gen Electric Compositions de liberation pour le papier adherant mieux au papier et aux films polymeres
US7090923B2 (en) 2003-02-12 2006-08-15 General Electric Corporation Paper release compositions having improved adhesion to paper and polymeric films
EP1980392A1 (fr) * 2003-02-12 2008-10-15 General Electric Company Compositions de papier détachable disposant d'une adhésion améliorée pour des films papier et polymériques
US7842394B2 (en) 2003-02-12 2010-11-30 Momentive Performance Materials Inc. Paper release compositions having improved adhesion to paper and polymeric films
US7767754B2 (en) 2005-11-08 2010-08-03 Momentive Performance Materials Inc. Silicone composition and process of making same
US7479522B2 (en) 2005-11-09 2009-01-20 Momentive Performance Materials Inc. Silicone elastomer composition
WO2009147283A1 (fr) * 2008-06-03 2009-12-10 Upm-Kymmene Corporation Composition de revêtement de démoulage, matériau de base et procédé de fabrication d'un matériau de base, et agent de traitement de surface pour matériau de base et utilisation d'un agent de traitement de surface
EP2300544B1 (fr) 2008-06-03 2016-02-10 UPM-Kymmene Corporation Composition de revêtement de démoulage, matériau de base et procédé de fabrication d'un matériau de base, et agent de traitement de surface pour matériau de base et utilisation d'un agent de traitement de surface
EP2574643A1 (fr) * 2008-06-03 2013-04-03 UPM-Kymmene Corporation Composition de couche de décolage, matériau de base et procédé de production d'un matériau de base, agent de traitement de surface pour un matériau de base et utilisation d'un agent de traitement de surface
EP2574644A1 (fr) * 2008-06-03 2013-04-03 UPM-Kymmene Corporation Composition de couche de décolage, matériau de base et procédé de production d'un matériau de base, agent de traitement de surface pour un matériau de base et utilisation d'un agent de traitement de surface
EP3009483A1 (fr) * 2008-06-03 2016-04-20 UPM-Kymmene Corporation Couche de décolage, matériau de base et procédé de production d'un matériau de base et utilisation d'un agent de traitement de surface
EP2574644B1 (fr) 2008-06-03 2016-02-10 UPM-Kymmene Corporation Composition de couche de décolage, matériau de base et procédé de production d'un matériau de base, agent de traitement de surface pour un matériau de base et utilisation d'un agent de traitement de surface
WO2010116045A1 (fr) * 2009-04-09 2010-10-14 Upm-Kymmene Corporation Procédé de traitement d'une surface d'un substrat
US8940372B2 (en) 2009-04-09 2015-01-27 Upm-Kymmene Corporation Method for treating a surface of a substrate
CN103254751A (zh) * 2011-07-12 2013-08-21 苏州斯迪克新材料科技股份有限公司 胶带用雾面离型膜的制作工艺
CN103254751B (zh) * 2011-07-12 2016-12-28 苏州斯迪克新材料科技股份有限公司 胶带用雾面离型膜的制作工艺
CN106221595A (zh) * 2016-07-21 2016-12-14 苏州泰仑电子材料有限公司 超轻离型力的离型膜及其制备方法

Also Published As

Publication number Publication date
CA2091083A1 (fr) 1993-10-01
US5415935A (en) 1995-05-16
DE69305101T2 (de) 1997-05-07
JPH0639970A (ja) 1994-02-15
JP2512858B2 (ja) 1996-07-03
KR930019401A (ko) 1993-10-18
EP0563704B1 (fr) 1996-10-02
DE69305101D1 (de) 1996-11-07

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